JP2000044733A - Luminous rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a luminous rubber composition with excellent emission luminance and an afterglow time. SOLUTION: This luminous rubber composition is obtained by blending a total of 100 pts.wt. of at least one synthetic rubber with 5-200 pts.wt. of at least one luminous fluorescence substance selected from SrAl2O4:Eu, Dy, Sr4Al14 O25:Eu, Dy, CaAl2O4:Eu, Nd, SrAl2O4:Eu and m(Sr1-xEux)O.nAl2O3.yB2O3 (wherein 1<=m<=5, 1<=n<=8, 0.001<=x<=0.1, 0.005<=y<=0.35), and crosslinking the resulting product with an organic peroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phosphorescent rubber composition, and more particularly, to a phosphorescent rubber composition having excellent emission luminance and afterglow characteristics.

[0002]

2. Description of the Related Art A large number of patents and utility models have been published that give rubber products such as tires, hoses, and oil fences luminous properties to improve visibility at night and in dark places, and to give design effects. (For example, Japanese Utility Model Laid-Open No. 7-37)
713, JP-A-59-20703, JP-A-7-148846, JP-A-8-318715 and JP-A-8-323926. However, in each case, a paint is applied to the surface of the rubber, or a light-storing material film in the form of a sheet is applied. .

There are patents in which a phosphor is kneaded into rubber (Japanese Patent Laid-Open Nos. 4-202339 and 8-2339).
38702, JP-A-8-269208 and JP-A-9-278931), as a practical matter, when an elastomer such as rubber is made to have a luminous property, rubber serving as a matrix transmits light to the luminous body. Since it is important to transmit light, carbon cannot be used for reinforcement. Also, if the elastomer is vulcanized with sulfur, the rubber will be colored yellow or ocher, or the heavy metal contained in the sulfur will impair the luminous brightness of the luminous body, and those with luminous properties that can withstand practical use are Had not been obtained.
In addition, a ZnS: Cu-based phosphorescent material that has been conventionally used is:
Both the emission luminance and the afterglow time are not satisfactory, and the use of radioactive elements mixed in to compensate for them has been a major problem in terms of safety and environment.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a strontium aluminate-based phosphorescent material or the like in a synthetic rubber and to crosslink with an organic peroxide to obtain excellent emission luminance and afterglow characteristics. An object of the present invention is to provide a phosphorescent rubber composition.

[0005]

According to the present invention, at least
To 100 parts by weight of a total of one or more synthetic rubbers,
Al_TwoO_Four: Eu, Dy, Sr_FourAl₁₄O_{twenty five}: Eu, D
y, CaAl_TwoO_Four: Eu, Nd, SrAl_TwoO_Four: E
u and m (Sr_1-xEu_x) OnAl_TwoO _Three・ YB
_TwoO_Three(1 ≦ m ≦ 5, 1 ≦ n ≦ 8, 0.001 ≦ x ≦
0.1, 0.005 ≦ y ≦ 0.35)
At least one kind of phosphorescent phosphor is blended in 5 to 200 parts by weight
And a phosphorescent rubber composition crosslinked with an organic peroxide is provided.
It is.

According to the present invention, the phosphorescent phosphor is characterized in that the phosphorescent phosphor has an average particle size of 1 to 100 μm, does not contain a radioactive substance, and is substantially free of carbon black. A functional rubber composition is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As the synthetic rubber used as the base material of the luminous rubber composition of the present invention, any rubber base material which is usually obtained may be used. For example, preferably, a diene rubber and a hydrogenated product thereof (for example, polyisoprene rubber (I
R), polybutadiene rubber (BR), conjugated diene-aromatic vinyl copolymer (for example, SBR), nitrile-conjugated diene copolymer (for example, NBR), hydrogenated NBR, hydrogenated SBR), olefin-based rubber (ethylene- Propylene rubber (EPDM or EPM), maleic acid-modified ethylene-propylene rubber (M-EPM), butyl rubber (II
R), isobutylene and aromatic vinyl or diene monomer copolymer), acrylic rubber (ACM), ionomer, halogen-containing rubber (for example, Cl-IIR, Br-II)
R, bromide of isobutylene-p-methylstyrene copolymer (Br-IPMS), chloroprene rubber (CR),
Hydrin rubber (CHR, CHC), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM),
Maleic acid-modified chlorinated polyethylene (M-CM)), sulfur-containing rubber (for example, polysulfide rubber), fluorine-containing rubber (for example, vinylidene fluoride-based rubber, fluorine-containing vinyl ether-based rubber, tetrafluoroethylene-propylene-based rubber, fluorine-containing phosphazene-based) Rubber), and these may be used alone or in combination of two or more. Halogen-containing rubber and butyl rubber are usually cross-linked with metal oxides (eg, zinc oxide, magnesium oxide, lead oxide, etc.), metal peroxides, or quinone dioximes. Is not used, so that the object of the present invention can be achieved without using an organic peroxide. This is, of course, within the scope of the present invention.

In the present invention, SrAl ₂ O ₄ : Eu, Dy, Sr ₄ Al ₁₄ O is used with respect to 100 parts by weight of the synthetic rubber.
₂₅ : Eu, Dy, CaAl ₂ O ₄ : Eu, Nd, SrA
l ₂ O ₄ : Eu and m (Sr ₁ -xE _x ) O · nAl
₂ O ₃ · yB ₂ O ₃ (1 ≦ m ≦ 5, 1 ≦ n ≦ 8, 0.0
01 ≦ x ≦ 0.1, 0.005 ≦ y ≦ 0.35) 5 to 200 parts by weight of at least one kind of phosphorescent phosphor selected from the group consisting of: The present invention is characterized in that a phosphorescent rubber composition is obtained. In the present invention, by using the specific phosphorescent phosphor, even without the presence of a radioactive element as in the related art, it is possible to provide emission luminance and afterglow time that are 10 times or more that of the related art. By cross-linking the rubber of the matrix with an organic peroxide, there is no coloring after vulcanization, and it is possible to suppress a decrease in luminance of the phosphorescent material.

The amount of the phosphorescent phosphor to be mixed with rubber is 5 parts by weight per 100 parts by weight of synthetic rubber.
It is indispensable to mix the luminous rubber composition having the function and effect of the present invention in order to obtain the luminous rubber composition having the effect of the present invention. If the compounding amount exceeds 200 parts by weight, the luminance is saturated. Therefore, if the compounding amount exceeds 200 parts by weight, not only is it wasteful, but also the physical properties of the obtained rubber composition deteriorate.

[0010] When the phosphorescent phosphor has an average particle diameter of 1 to 100 µm, it exerts more favorable effects. If the particle size is less than 1 μm, classification becomes difficult and the brightness decreases, and if it exceeds 100 μm, the physical properties of the rubber composition deteriorate.

As the organic peroxide used for crosslinking the rubber material in the present invention, those used for ordinary peroxide vulcanization of rubber can be used. For example, dicumyl peroxide, di-t-butyl peroxide, t
-Butylcumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-mono (t-butylperoxy) hexane,
α, α'-bis (t-butylperoxy-m-isopropyl) benzene and the like. One or more of these organic peroxides are used, and it is desirable to add 0.2 to 10 parts by weight, preferably 0.2 to 6 parts by weight, per 100 parts by weight of rubber.

In the luminous rubber composition of the present invention, silica, talc, clay, charcoal and the like as white fillers can be appropriately blended in a usual blending amount depending on required physical properties. In addition, fillers such as silica or glass powder, quartz powder, and acrylic resin powder are used to irregularly reflect the light of the phosphorescent phosphor to increase light emission luminance and enhance visibility, and impede light transmission or impair physical properties. It can be blended to an extent that it is not noticeable. Alternatively, a sheet containing these light reflecting materials may be separately prepared and laminated with the luminous rubber composition of the present invention. However, the addition of carbon black as a filler is not preferable because the light emission luminance of the phosphorescent material is significantly impaired. Further, it is preferable that heavy metals (Co, Ni, Pb, Ti, Cd, etc.) and a compound having high hygroscopicity which lower the luminance of the phosphorescent material, and a compounding agent having coloring and contamination are not compounded.

The luminous rubber composition of the present invention is a product excellent in visibility in a dark place, at night or the like, and an elastomer product having a design effect, for example, a tire, a hose, a marine hose, a fender, a track belt. , Conveyor belts, soles,
Rubber boots, ball balls, contraceptives, rubber fences, stationery, wetsuits, fins for diving, fins for underwater glasses, motorcycles, bicycles, etc. .

[0014]

EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples, but it goes without saying that the scope of the present invention is not limited to these Examples.

The following commercially available products were used as the components used in the following examples and comparative examples. NR (Natural rubber): RSS # 3 SBR: Nipol 1502 (Zeon, Japan) IR: Nipol IR-2200 (Zeon, Japan) EPDM: Mitsui EPT4070 (Mitsui Petrochemical) Br-IIR: Exxon Brobutyl 2255 (Nippon Butyl) Carbon: HTC-100 (Chubu Carbon) Silica: Nipsil AQ (Nippon Silica Kogyo) Silane coupling: Si-69 (Degussa) ZnO: Zinc flower # 1 (Seido Kagaku) Stearic acid: Beads stearic acid (Nippon Yushi) Aging Inhibitor: Antage W-400 (Kawaguchi Chemical) Sulfur: Sunfel (Sanshin Chemical Industry) Vulcanization accelerator: Noxeller NS-F (Ouchi Shinko Chemical) Organic peroxide: Parkadox 14/40 (explosive powder Akzo) ZnS : Cu: (Nemoto Specialty Chemicals) Sr _{l 2 O 4: Eu, Dy} : Ruminoba G-300 (Nemoto)

Examples 1 to 5 and Comparative Examples 1 to 4 The respective components were blended according to the blending contents (parts by weight) shown in Table 1, and the raw material rubber and the blending excluding the vulcanization accelerator and sulfur or organic peroxide were added. The mixture was mixed with a 1.7 liter Banbury mixer for 5 minutes, and then a vulcanization accelerator and sulfur or an organic peroxide were added to the mixture, and the mixture was kneaded with an 8-inch test kneading roll machine for 4 minutes to obtain a rubber composition. I got something. Each of these rubber compositions was press-vulcanized at 160 ° C. for 20 minutes to prepare a target test piece, which was subjected to a test of the luminance.
Table 1 shows the obtained test results.

The test method of emission luminance is based on JIS Z
The test piece was irradiated with 200 lux of light for 10 minutes using a common light source D ₆₅ specified in 8720, and the luminance was visually checked after 10 minutes and 1 hour. The results were evaluated according to the following evaluation criteria. The evaluation was based on the following. ◎: Very bright ○: Bright △: Dark but light can be confirmed ×: Light cannot be confirmed

[0018]

[Table 1]

According to the results shown in Table 1, in Comparative Example 1 in which the luminous material of the present invention was blended with NR (natural rubber),
It can be seen that the brightness is low because the color itself is brown. Also,
Even when the phosphorescent material of the present invention was used for synthetic rubber (SBR), in Comparative Example 2 of sulfur vulcanization, the rubber was colored yellow, and the brightness was reduced due to the influence of Pb in sulfur. In Comparative Example 3, the rubber was colored black, and no light emission was observed. In Comparative Example 4 where a conventional zinc sulfide-based phosphorescent material was used for synthetic rubber (SBR),
Both the luminance and the afterglow time were insufficient. In comparison with these, in Examples 1 to 4 of the present invention, the brightness was high, the afterglow time was long, and good results were obtained. Further, in Example 5 where the amount of the phosphorescent material of the present invention was increased, the luminance was further improved.

[0020]

According to the present invention, a predetermined amount of a strontium aluminate-based phosphorescent material is mixed with synthetic rubber and crosslinked with an organic peroxide, whereby a phosphorescent rubber composition having excellent emission luminance and afterglow time can be obtained. The phosphorescent rubber composition is used in a dark place,
It can be effectively used for various elastomer-applied products that have excellent visibility at night and have a design effect.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuichi Hara 2-1 Oiwake, Hiratsuka-shi, Kanagawa Prefecture Yokohama Rubber Co., Ltd. Inside the Hiratsuka Factory (72) Inventor Yoshihiro Soeda 2-1 Oiwake, Hiratsuka-shi, Kanagawa Prefecture Yokohama Rubber Co., Ltd. F-term in Hiratsuka Factory (reference)

Claims (3)

[Claims] A total of at least one kind of synthetic rubber
100 parts by weight of SrAl_TwoO_Four: Eu, Dy, Sr_Four
Al₁₄O_{twenty five}: Eu, Dy, CaAl_TwoO_Four: Eu, N
d, SrAl_TwoO_Four: Eu and m (Sr_1-xEu_x)
O ・ nAl_TwoO _Three・ YB_TwoO_Three(1 ≦ m ≦ 5, 1 ≦ n ≦
8, 0.001 ≦ x ≦ 0.1, 0.005 ≦ y ≦ 0.3
5) at least one kind of phosphorescent phosphor selected from 5)
~ 200 parts by weight and crosslinking with organic peroxide
A phosphorescent rubber composition, characterized by: 2. The phosphorescent phosphor has an average particle diameter of 1 to 1.
The luminous rubber composition according to claim 1, wherein the luminous rubber composition has a thickness of 00 µm and does not contain a radioactive substance. 3. The phosphorescent rubber composition according to claim 1, wherein the rubber composition does not substantially contain carbon black.